CN107418141B - Resin composition for cleaning mold - Google Patents

Resin composition for cleaning mold Download PDF

Info

Publication number
CN107418141B
CN107418141B CN201710156947.5A CN201710156947A CN107418141B CN 107418141 B CN107418141 B CN 107418141B CN 201710156947 A CN201710156947 A CN 201710156947A CN 107418141 B CN107418141 B CN 107418141B
Authority
CN
China
Prior art keywords
cleaning
resin composition
mold
mass
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710156947.5A
Other languages
Chinese (zh)
Other versions
CN107418141A (en
Inventor
福西阳一
弘光清人
野村弘明
吉村胜则
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Carbide Industries Co Inc
Original Assignee
Nippon Carbide Industries Co Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Carbide Industries Co Inc filed Critical Nippon Carbide Industries Co Inc
Publication of CN107418141A publication Critical patent/CN107418141A/en
Application granted granted Critical
Publication of CN107418141B publication Critical patent/CN107418141B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/70—Maintenance
    • B29C33/72—Cleaning
    • B29C33/722—Compositions for cleaning moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/1753—Cleaning or purging, e.g. of the injection unit
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C08K5/31—Guanidine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Detergent Compositions (AREA)

Abstract

The present invention relates to a resin composition for mold cleaning, which contains a melamine resin, a fatty acid zinc and an organic base (wherein salts formed by strong acid and weak base are not included), wherein the content of the fatty acid zinc is more than 1 part by mass relative to 100 parts by mass of the total solid content of the resin composition for mold cleaning, and the ratio of the content of the organic base relative to the content of the fatty acid zinc is 1/100-1/2 by mass.

Description

Resin composition for cleaning mold
Technical Field
The present invention relates to a resin composition for cleaning a mold.
Background
If the molding operation of the package molding product such as an integrated circuit or an led (light Emitting diode) element is continued for a long time using the package molding material containing a thermosetting resin, dirt from the package molding material adheres to the inner surface of the molding die. If the dirt adhering to the inner surface of the molding die is left alone, there is a problem that the dirt adheres to the surface of the molded package such as an integrated circuit or an LED element. In order to prevent such a problem, the molding die needs to be periodically cleaned. As a method of cleaning a molding die, a method of using a resin composition for die cleaning is known.
For example, international publication No. 2002/030648 discloses a resin composition for mold cleaning, which contains a melamine resin and a fibrous inorganic compound having a specific average fiber length, average fiber diameter and aspect ratio.
Japanese patent application laid-open No. 1-139649 discloses a resin composition for mold cleaning containing a melamine resin and a guanidine derivative.
Disclosure of Invention
In recent years, a green compound-called encapsulating molding material containing no halogen-based flame retardant or the like has been used in order to cope with environmental problems. In the molding using the green composite, the mold is easily contaminated, and the adhered dirt is difficult to remove, so that the cleaning performance of the conventional resin composition for cleaning the mold cannot be sufficiently satisfied. Therefore, development of a resin composition for mold cleaning having higher cleaning performance than ever has been desired.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin composition for mold cleaning having excellent cleaning performance.
Specific methods for solving the problems include the following methods.
< 1 > A resin composition for mold cleaning, which contains a melamine resin, a fatty acid zinc and an organic base (wherein salts formed by strong acid and weak base are not included), wherein the content of the fatty acid zinc is 1 part by mass or more per 100 parts by mass of the total solid content of the resin composition for mold cleaning, and the ratio of the content of the organic base to the content of the fatty acid zinc is 1/100-1/2 on a mass basis.
< 2 > the resin composition for mold cleaning as < 1 >, wherein the above organic base is at least 1 compound selected from the group consisting of guanidine compounds and amidine compounds.
< 3 > such as < 1 > or < 2 >, wherein the fatty acid zinc contains at least one selected from the group consisting of zinc myristate and zinc stearate.
The resin composition for mold cleaning of any one of < 4 > to < 1 > -3 > wherein the melamine resin contains a melamine-formaldehyde resin.
According to the present disclosure, a resin composition for mold cleaning having excellent cleaning performance can be provided.
Detailed Description
The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the object of the present invention.
In the present specification, the numerical range expressed by the term "to" means a range including the numerical values described before and after the term "to" as the minimum value and the maximum value, respectively.
In the present specification, the amount of each component in the resin composition refers to the total amount of a plurality of substances present in the resin composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the resin composition.
In the present specification, the "inner surface of the molding die" refers to a region in contact with the object to be molded by the molding die.
[ resin composition for cleaning mold ]
The resin composition for mold cleaning comprises a melamine resin, a fatty acid zinc and an organic base (wherein salts formed by strong acid and weak base are not included; hereinafter, also simply referred to as "organic base"), wherein the content of the fatty acid zinc is 1 part by mass or more per 100 parts by mass of the total solid content of the resin composition for mold cleaning, and the ratio of the content of the organic base to the content of the fatty acid zinc is 1/100-1/2 on a mass basis.
The resin composition for cleaning a mold disclosed by the invention has better cleaning performance than the conventional resin composition for cleaning a mold.
The reason why the resin composition for mold cleaning disclosed in the present invention can achieve such an effect is not clear, but the inventors of the present invention presume as follows.
Generally, a resin composition for cleaning a mold, which contains a melamine resin, contains a fatty acid zinc such as zinc stearate or zinc myristate for the purpose of improving the cleaning performance of the mold, the releasability from the mold after cleaning, and the tabletability. Examples of the resin composition for cleaning a mold, which contains zinc stearate, are disclosed in, for example, the above-mentioned international publication No. 2002/030648 and japanese patent application laid-open No. 1-139649.
From the viewpoint of further improving the cleaning performance of the molding die, the mold releasability in the molding die after cleaning, the tableting property, and the like, it is preferable that the resin composition for cleaning a die containing a melamine resin contains as much fatty acid zinc as possible.
However, since zinc fatty acid as an acidic compound can function as an acidic catalyst for the curing reaction of a melamine resin, if an excessive amount of zinc fatty acid is contained in a mold cleaning resin composition containing a melamine resin, the curing reaction of the melamine resin is accelerated, and the cleaning performance of a molding mold tends to be deteriorated.
The resin composition for cleaning a mold comprises a melamine resin, a fatty acid zinc, and an organic base (wherein salts formed by a strong acid and a weak base are not included), and the ratio of the content of the organic base to the content of the fatty acid zinc is 1/100-1/2 on a mass basis, so that the curing reaction of the melamine resin using the fatty acid zinc can be controlled to an appropriate speed by the organic base. Thus, by controlling the curing reaction of the melamine resin with the fatty acid zinc at an appropriate rate by the organic base, the resin composition for mold cleaning can contain a sufficient amount of the fatty acid zinc for improving the cleaning performance of the molding mold, that is, 1 part by mass or more per 100 parts by mass of the total solid content of the resin composition for mold cleaning. As a result, it is considered that the resin composition for cleaning a mold disclosed in the present invention can achieve excellent cleaning performance.
As described above, the resin composition for mold cleaning according to the present invention can contain a sufficient amount for improving releasability from a cleaned molding die, that is, 1 part by mass or more of fatty acid zinc per 100 parts by mass of the total solid content of the resin composition for mold cleaning, and therefore, the resin composition for mold cleaning is excellent in workability when a molded product of the resin composition for mold cleaning after cleaning is removed from the molding die.
[ Melamine-based resin ]
The resin composition for cleaning a mold comprises a melamine resin.
The resin composition for cleaning a mold disclosed in the present invention contains a melamine resin, and thus can exhibit excellent cleaning performance for dirt on the inner surface of a molding mold.
Melamine-based resins are considered to have highly polar methylol groups which act on stains derived from an encapsulating molding material containing a thermosetting resin composition such as an epoxy resin and thereby to achieve an excellent cleaning performance effect. Further, the melamine resin is stable against heat, and therefore, the resin composition for mold cleaning disclosed in the present invention is considered to exhibit stable cleaning performance even at a temperature of about 160 ℃ to 190 ℃ which is a normal temperature at the time of mold cleaning.
In the present disclosure, "melamine-based resin" refers to a melamine resin, a melamine-phenol cocondensate, or a melamine-urea cocondensate.
In the present disclosure, 1 or more of them are selectively used.
The melamine resin is a condensate of a triazine compound and an aldehyde compound.
Examples of the triazine compound include melamine, benzoguanamine, and methylguanamine.
Examples of the aldehyde compound include formaldehyde, paraformaldehyde, and acetaldehyde.
The melamine resin preferably has a molar ratio of repeating units derived from a triazine compound to repeating units derived from an aldehyde compound of 1: 1.2-1: 4.
in the present specification, a condensate of melamine and formaldehyde is referred to as a melamine-formaldehyde resin.
The melamine-phenol cocondensate is a cocondensate of a triazine compound with a phenol compound and an aldehyde compound.
Examples of the phenol compound include phenol, cresol, xylenol, ethylphenol, and butylphenol.
The melamine-phenol cocondensate preferably has a molar ratio of repeat units from the triazine compound to repeat units from the phenol compound to repeat units from the aldehyde compound of 1: 0.3: 1-1: 1: 3.
the melamine-urea cocondensate is a cocondensate of a triazine compound with a urea compound and an aldehyde compound.
Examples of the urea compound include urea, thiourea, and ethylene urea.
In the melamine-phenol co-condensation resin and the melamine-urea co-condensation resin, the amount of the triazine compound and the phenol compound in the raw materials is, for example, 30 mass% or more, 40 mass% or more, 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, or 90 mass% or more and less than 100 mass% in the total amount of the triazine compound and the phenol compound in the raw materials or in the total amount of the triazine compound and the urea compound in the raw materials.
The resin composition for mold cleaning disclosed in the present invention may contain, in addition to the melamine-based resin, other types of resins, for example, one or more selected from alkyd resins, polyester resins, acrylic resins, epoxy resins, and rubbers, within a range not impairing the effects of the present invention.
The melamine resin disclosed in the present invention can be produced by a known method.
For example, melamine resin is prepared by mixing melamine crystals and formaldehyde in a molar ratio of 1: 1.2-1: 4 at a reaction temperature of 80 to 90 ℃ and a pH of 7 to 7.5, and then reacting at 60 ℃ until an aqueous solution of 3 mass% of the reaction product becomes cloudy. Next, sodium hydroxide was added thereto and cooled to obtain a melamine resin.
Commercially available melamine resins can be used.
Examples of commercially available products include Nikarein (registered trademark) S-166, S-176, S-260, and S-305 from Tokyo carbide industries, Ltd.
The resin composition for cleaning a mold disclosed in the present invention may contain only 1 melamine resin, or may contain 2 or more melamine resins.
The content of the melamine resin in the resin composition for mold cleaning disclosed in the present invention is not particularly limited. For example, the content of the melamine resin in the resin composition for mold cleaning is preferably 55 to 85 parts by mass, more preferably 60 to 80 parts by mass, and still more preferably 65 to 75 parts by mass, based on 100 parts by mass of the total solid content of the resin composition for mold cleaning.
[ Zinc fatty acid salt ]
The resin composition for mold cleaning disclosed by the invention contains 1 part by mass or more of fatty acid zinc per 100 parts by mass of the total solid content of the resin composition for mold cleaning.
The zinc fatty acid is useful for improving the mold cleaning performance, the releasability from the mold after cleaning, and the tabletability of the mold in the resin composition for mold cleaning disclosed in the present invention.
The fatty acid zinc is not particularly limited.
The fatty acid constituting the fatty acid zinc may be either a saturated fatty acid or an unsaturated fatty acid, and is preferably a saturated fatty acid.
The fatty acid constituting the fatty acid zinc is preferably a saturated fatty acid having 12 to 20 carbon atoms, and more preferably a saturated fatty acid having 14 to 18 carbon atoms.
Specific examples of the saturated fatty acid having 12 to 20 carbon atoms include lauric acid having 12 carbon atoms (IUPAC name: dodecanoic acid), myristic acid having 14 carbon atoms (IUPAC name: tetradecanoic acid), palmitic acid having 16 carbon atoms (IUPAC name: hexadecanoic acid), stearic acid having 18 carbon atoms (IUPAC name: octadecanoic acid), and arachidic acid having 20 carbon atoms (IUPAC name: eicosanoic acid).
The fatty acid zinc is preferably at least 1 selected from zinc myristate composed of saturated fatty acids having 14 carbon atoms and zinc stearate composed of saturated fatty acids having 18 carbon atoms and zinc, and is particularly preferably zinc myristate.
The resin composition for cleaning a mold disclosed in the present invention may contain only 1 kind of zinc fatty acid, or may contain 2 or more kinds.
The content of fatty acid zinc in the resin composition for mold cleaning disclosed in the present invention is 1 part by mass or more, preferably 1.2 parts by mass or more, and more preferably 1.5 parts by mass or more, per 100 parts by mass of the total solid content of the resin composition for mold cleaning.
When the content of the fatty acid zinc is 1 part by mass or more per 100 parts by mass of the total solid content of the resin composition for mold cleaning, excellent cleaning performance is exerted on the dirt on the inner surface of the molding die. Further, the release of the molded product of the resin composition for mold cleaning after cleaning from the inner surface of the molding die becomes good, and the workability when the molded product is removed from the molding die is improved. Further, the sheeting property in the sheeting and molding of the composition for cleaning a mold disclosed in the present invention is improved.
As described above, the zinc fatty acid contributes not only to improvement of cleaning performance of the mold but also to improvement of releasability from the mold after cleaning, tableting performance, and the like. However, when the resin composition for mold cleaning containing a melamine resin contains an excessive amount of zinc fatty acid, the sheeting property may be rather deteriorated, or excessive zinc fatty acid may remain in the molding die to contaminate the molding die. Further, it is considered that the releasability from the mold after cleaning does not change much even if the content of zinc fatty acid in the resin composition for mold cleaning exceeds a certain amount, and therefore the advantage of excessively containing zinc fatty acid is small.
The upper limit of the content of the fatty acid zinc in the resin composition for mold cleaning disclosed in the present invention is not particularly limited, and is preferably 5 parts by mass or less, and more preferably 4 parts by mass or less, based on 100 parts by mass of the total solid content of the resin composition for mold cleaning, for example, from the viewpoint of preventing a decrease in tableting property and contamination of a molding die.
[ organic base ]
The resin composition for cleaning a mold contains an organic base (excluding salts formed from strong acids and weak bases). In the resin composition for cleaning a mold, the ratio of the content of the organic base to the content of the zinc fatty acid is 1/100 to 1/2 on a mass basis.
In the resin composition for cleaning a mold disclosed in the present invention, the organic base contributes to control of the curing reaction rate of the melamine resin using the fatty acid zinc.
The organic base is not particularly limited as long as it is not a salt of a strong acid and a weak base.
Examples of the organic base include guanidine compounds (guanidine carbonate, aminoguanidine bicarbonate, guanidine phosphate, 1,3, 3-tetramethylguanidine, phenylguanidine, etc.), amidine compounds (1, 8-diazabicyclo [5.4.0] -7-undecene, 1, 5-diazabicyclo [4.3.0] -5-nonene, etc.), and the like.
Among these, the organic base is preferably at least 1 compound selected from guanidine compounds and amidine compounds, more preferably at least 1 compound selected from guanidine carbonate, aminoguanidine bicarbonate and 1, 8-diazabicyclo [5.4.0] -7-undecene, and even more preferably guanidine carbonate, from the viewpoint of effectively suppressing the increase in the curing reaction rate of the melamine resin using fatty acid zinc described above.
The salt of a strong acid and a weak base is a salt of an acid having a pKa of 2.0 or less at a temperature of 25 ℃ and a base having a pKb of 3.0 to 11.0 at a temperature of 25 ℃. Here, "Ka" is a dissociation constant of an acid, "Kb" is a dissociation constant of a base, pKa ═ logKa, pKb ═ logKb.
Examples of the salt of a strong acid with a weak base include salts of a strong acid represented by hydrochloric acid, sulfuric acid, and nitric acid with a weak base represented by ammonia, diethanolamine, triethanolamine, and aniline.
The resin composition for cleaning a mold disclosed in the present invention may contain only 1 type of organic base, or may contain 2 or more types.
The content of the organic base in the resin composition for mold cleaning disclosed in the present invention is preferably 0.01 to 2.5 parts by mass, more preferably 0.012 to 2.0 parts by mass, and further preferably 0.015 to 1.5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition for mold cleaning.
In the resin composition for mold cleaning disclosed by the invention, the ratio of the content of the organic base to the content of the fatty acid zinc is 1/100 to 1/2, preferably 1/80 to 1/3, and more preferably 1/40 to 1/4 on a mass basis.
When the ratio of the content of the organic base to the content of the zinc fatty acid is 1/100 or more by mass, the increase in the curing reaction rate of the melamine resin using the zinc fatty acid can be controlled by the organic base, and therefore the resin composition for mold cleaning can contain the zinc fatty acid in an amount sufficient for improving the cleaning performance of the molding mold, that is, 1 part by mass or more per 100 parts by mass of the total solid content of the resin composition for mold cleaning. As a result, the resin composition for cleaning a mold disclosed in the present invention can achieve excellent cleaning performance.
When the ratio of the content of the organic base to the content of the zinc fatty acid is 1/2 or less on a mass basis, the zinc fatty acid functions moderately as an acid catalyst for the melamine resin, and therefore the moldability of the resin composition for mold cleaning becomes good.
[ other Components ]
The resin composition for mold cleaning disclosed in the present invention may contain additives such as a filler, a lubricant, a colorant, and an antioxidant as needed within a range not impairing the effects disclosed in the present invention, in addition to the melamine resin, the fatty acid zinc, and the organic base (excluding salts formed by strong acids and weak bases).
< filling Material >
The resin composition for cleaning a mold disclosed in the present invention preferably contains a filler.
If the resin composition for cleaning a mold contains a filler, the strength of the resin composition for cleaning a mold is appropriately maintained at the time of molding, and therefore, the workability when the molded product of the resin composition for cleaning a mold is removed from the molding die after cleaning becomes better, and the cleaning performance of the inner surface of the molding die also becomes better.
The filler may be any of an organic filler and an inorganic filler.
(organic Filler)
Examples of the organic filler include pulp, wood powder, and synthetic fibers.
Among these, pulp is particularly preferable as the organic filler.
Examples of the pulp include wood pulp (softwood pulp, hardwood pulp, etc.), non-wood pulp (straw, bamboo, bagasse, cotton, etc.), and the like. These pulps may be either of chemical pulp and mechanical pulp.
The size of the pulp is not particularly limited, and is, for example, preferably 5 to 1000 μm, and more preferably 10 to 200 μm in terms of fiber length. The fiber length of the pulp can be measured, for example, by a method prescribed in JIS P8226-2 in accordance with ISO 16065-2.
When the size of the pulp is within the above range, the fluidity of the resin composition for mold cleaning is good, and thus the resin composition can be sufficiently cleaned up to the corner portion of the cavity of the molding die. Further, if the size of the pulp is within the above range, the strength of the resin composition for mold cleaning is appropriately maintained at the time of molding, and therefore, the workability when cleaning the molded product of the resin composition for mold cleaning from the molding die after cleaning becomes better, and the cleaning performance of the inner surface of the molding die also becomes better.
When the resin composition for mold cleaning disclosed in the present invention contains an organic filler, only 1 type of organic filler may be contained, or 2 or more types may be contained.
When the resin composition for mold cleaning disclosed in the present invention contains an organic filler, the content of the organic filler in the resin composition for mold cleaning is preferably 3 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the resin composition for mold cleaning.
When the content of the organic filler is within the above range, the fluidity of the resin composition for mold cleaning is more appropriate. Further, if the content of the organic filler is within the above range, the strength of the resin composition for mold cleaning can be appropriately maintained at the time of molding, and therefore, the workability at the time of cleaning the molded product of the resin composition for mold cleaning from the molding die after cleaning becomes better, and the cleaning performance of the inner surface of the molding die also becomes better.
(inorganic Filler)
Examples of the inorganic filler include silicon carbide, silicon oxide (silica), titanium carbide, titanium oxide, boron carbide, boron oxide, aluminum oxide, magnesium oxide, calcium oxide, and calcium carbonate.
Among these, as the inorganic filler, at least 1 kind selected from the group consisting of silicon carbide, silicon oxide (silica), titanium carbide, titanium oxide, boron carbide, boron oxide, aluminum oxide, magnesium oxide, and calcium oxide is preferable from the viewpoint of being well mixed with the melamine resin when the resin composition for mold cleaning is prepared.
Further, the inorganic filler is more preferably at least 1 selected from silicon oxide (silica) and titanium oxide, and particularly preferably silicon oxide (silica).
However, it is preferable that the hardness of silicon oxide (silica) or titanium oxide is appropriate, so that the occurrence of abrasion and scratch on the inner surface of the molding die and the gate portion can be suppressed, and the molding die is thermally stable even at a temperature of about 160 ℃ to 190 ℃ which is a normal temperature at the time of cleaning the molding die.
In addition, regarding the hardness (new mohs hardness) of the above exemplified inorganic filler, silicon carbide is 13, silicon oxide (silica) is 8, titanium carbide is 9, titanium oxide is 8, boron carbide is 14, boron oxide is 3, aluminum oxide is 12, magnesium oxide is 4, and calcium oxide is 3.
As the inorganic filler, commercially available products can be used.
Examples of commercially available products include amorphous silica such as "S440-4", "HS-202", "HS-204", "UF-320" (trade names) available from MICRON corporation, Nippon iron-based materials, and crystalline silica such as pure silica powder (trade name) available from Ciba kiln industry raw materials.
When the resin composition for mold cleaning disclosed in the present invention contains an inorganic filler, only 1 kind of inorganic filler may be contained, or 2 or more kinds may be contained.
When the resin composition for mold cleaning disclosed in the present invention contains an inorganic filler, the content of the inorganic filler in the resin composition for mold cleaning is preferably 10 to 30 parts by mass, and more preferably 15 to 25 parts by mass, based on 100 parts by mass of the total solid content of the resin composition for mold cleaning.
When the content of the inorganic filler is within the above range, the strength of the resin composition for mold cleaning can be appropriately maintained at the time of molding, and therefore, the workability at the time of cleaning the molded product of the resin composition for mold cleaning from the molding die after cleaning becomes better, and the cleaning performance of the inner surface of the molding die also becomes better.
< Lubricant >)
The resin composition for cleaning a mold disclosed in the present invention preferably contains a lubricant.
When the resin composition for cleaning a mold contains a lubricant, the dispersibility of each component is improved in the production of the resin composition for cleaning a mold.
Examples of the lubricant include fatty acid amide-based lubricants, and specifically include saturated or unsaturated monoamide-based lubricants such as lauric acid amide, myristic acid amide, erucic acid amide, oleic acid amide, and stearic acid amide, and saturated or unsaturated bisamide-based lubricants such as methylene bisstearic acid amide, ethylene bisstearic acid amide, and ethylene bisoleic acid amide.
When the resin composition for cleaning a mold according to the present invention contains a lubricant, it may contain only 1 kind of lubricant, or may contain 2 or more kinds of lubricants.
When the resin composition for mold cleaning disclosed in the present invention contains a lubricant, the content of the lubricant in the resin composition for mold cleaning is preferably 0.1 to 0.6 parts by mass, and more preferably 0.2 to 0.5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition for mold cleaning.
[ method for producing resin composition for mold cleaning ]
The resin composition for mold cleaning disclosed in the present invention can be prepared, for example, by mixing a melamine resin, fatty acid zinc, and an organic base (excluding salts formed from strong acids and weak bases), and other components already described as necessary.
The mixing method is not particularly limited, and a known mixing method using a kneader, a ribbon mixer, a nauta mixer, a henschel mixer, a ball mill, a roll mill, a kneader, a roll, or the like can be mentioned.
[ use ]
The resin composition for mold cleaning disclosed in the present invention is suitably used for removing dirt from the inner surface of a molding die from a sealing molding material containing a thermosetting resin such as an epoxy resin, a silicone resin, a melamine resin, a urea resin, a phenol resin, or a polyimide resin.
The resin composition for cleaning a mold disclosed in the present invention is particularly preferably a so-called transfer-type resin composition for cleaning a mold, which cleans the inner surface of a molding die by transfer molding.
[ mold cleaning method ]
The resin composition for mold cleaning disclosed in the present invention is usually processed into a tablet form and used for cleaning the inner surface of a molding die. Specifically, after a lead frame is placed on a molding die, a tablet-shaped resin composition for die cleaning is inserted into a pot portion and clamped, and then the tablet-shaped resin composition is pressed by a plunger. At this time, the resin composition for mold cleaning in the pot portion flows into the cavity through the gate portion via the runner portion. After a predetermined molding time has elapsed, the mold is opened, and the molded article integrated with the lead frame, that is, the molded article of the mold-cleaning resin composition containing the dirt is removed.
Examples
The present disclosure will be described in more detail with reference to the following examples. The present invention is not limited to the following examples as long as the disclosure does not exceed the gist thereof.
[ preparation of Melamine-Formaldehyde resin containing pulp ]
[ production example 1 ]
A melamine-formaldehyde resin is obtained by heating and reacting 346 parts by mass of melamine with 522 parts by mass of formaldehyde (37 mass% aqueous solution) at a heating temperature of 70-100 ℃ and a pH of 8-10 for 90 minutes. To the obtained melamine-formaldehyde resin, 95 parts by mass of broadleaf tree pulp (trade name: LDPT, japan paper company) as an organic filler was added and kneaded, and then, the kneaded mixture was dried under reduced pressure and powdered to obtain a pulp-containing melamine-formaldehyde resin having a pulp content of 15 mass%.
[ preparation of resin composition for mold cleaning ]
[ example 1 ]
30 parts by mass of the pulp-containing melamine-formaldehyde resin obtained as described above as a melamine resin, 50 parts by mass of Nikarein (registered trademark) S-166 (trade name, melamine-formaldehyde resin, Nippon calcium carbide industries, Ltd.), 20 parts by mass of silica (trade name: pure silica Powder, crystalline silica, Kikuchi Kogyo Co., Ltd.) as an inorganic filler, 1 part by mass of zinc myristate (trade name: Powder base M, Nikukoku Co., Ltd.) as a fatty acid zinc, and 0.025 part by mass of guanidine carbonate (trade name: GC, Kabushiki Kaisha Co., Ltd.) as an organic base were charged into a ball mill and pulverized. Then, 0.4 parts by mass of ethylene bis stearamide (trade name: ALFLOW (registered trade name) H50T, Nichigan oil Co., Ltd.) was added as a lubricant to a nauta mixer and stirred to obtain the resin composition for cleaning a mold of example 1.
[ example 2 to example 8 ]
Resin compositions for cleaning molds of examples 2 to 8 were obtained in the same manner as in example 1, except that the composition of the resin composition for cleaning molds in example 1 was changed to the composition shown in table 1 below.
[ comparative examples 1 to 6 ]
Resin compositions for cleaning molds of comparative examples 1 to 6 were obtained in the same manner as in example 1, except that the composition of the resin composition for cleaning molds in example 1 was changed to the composition shown in table 2 below.
[ evaluation ]
The mold cleaning resin compositions of examples 1 to 8 and comparative examples 1 to 6 were evaluated for cleanability and moldability by the methods shown below.
(1) Cleaning property
The resin composition for mold cleaning was molded into a tablet form to prepare a sample for evaluation.
QFP (quad Flat Package) having a gate part with a width of 800 μm and a height of 300 μm was injection-molded 600 times (shot) using a commercially available epoxy resin molding material (trade name: CEL-9240 HF10, green compound, Hitachi chemical Co., Ltd.) using a transfer automatic molding machine under molding conditions of a mold temperature of 175 ℃, a transfer pressure of 9.5MPa, a transfer time of 10.5 seconds, and a curing time of 80 seconds, and fouling was generated on the inner surface of the molding mold.
Using the molding die having a contaminant on the inner surface, the resin compositions of examples and comparative examples were repeatedly molded under the same molding conditions as described above, and die cleaning was performed. Then, the number of times of injection molding required until the contaminants present on the inner surface of the molding die could be completely removed was measured. The number of times of injection molding was used as an index for evaluating cleanability of the resin composition for mold cleaning. To visually confirm and judge whether or not the contaminants can be completely removed.
In evaluating the cleaning performance, attention is paid particularly to whether or not contaminants adhering to the gate portion and the corner portion of the cavity of the molding die can be removed. The smaller the number of shots, the more excellent the cleaning performance. In this evaluation, the resin composition having the injection molding frequency of 1 was judged as "acceptable".
(2) Formability
The workability when the mold-cleaning resin composition after the 1 st injection molding (after cleaning) in the above-described evaluation of the 1 st cleanability was removed from the molding die was taken as an index for evaluating the moldability of the mold-cleaning resin composition.
The moldability of the mold-cleaning resin composition was evaluated as "good" when the molded mold-cleaning resin composition was sufficiently cured, no contamination substances from the mold-cleaning resin composition partially adhered to the inner surface of the molding die due to poor curing occurred, and the mold-cleaning resin composition could be easily removed from the molding die after cleaning. In addition, when the resin composition for cleaning a mold after molding is not sufficiently cured and a part thereof is not molded, and thus the resin composition for cleaning a mold is stuck to the inner surface of the molding mold or the like, and the resin composition for cleaning a mold cannot be easily removed from the molding mold after cleaning, the moldability of the resin composition for cleaning a mold is evaluated as "poor".
The compositions of the resin compositions for mold cleaning of examples 1 to 8 and comparative examples 1 to 6 and the respective evaluation results are shown in tables 1 and 2.
Figure BDA0001247343550000151
Figure BDA0001247343550000161
In tables 1 and 2, "-" means that there is no corresponding composition.
The details of zinc stearate and potassium stearate in tables 1 and 2 are as follows.
Zinc stearate (trade name: ZINC STEARATE GF200, Nichiya oil Co., Ltd.)
Potassium stearate (trade name: Nonsoul (registered trademark) SK-1, Nichio oil Co., Ltd.)
As is clear from the results in tables 1 and 2, the resin compositions for mold cleaning of examples 1 to 8 have superior cleaning performance as compared with the resin compositions for mold cleaning of comparative examples 1 to 6. It is also clear that the resin compositions for mold cleaning of examples 1 to 8 are excellent in moldability. If the moldability of the resin composition for mold cleaning is good, the resin composition for mold cleaning can be easily removed from the molding die after cleaning, and therefore the workability becomes good.
On the other hand, it was found that the mold cleaning resin composition of comparative example 1, in which the content of zinc fatty acid was less than 1 part by mass per 100 parts by mass of the total solid content of the mold cleaning resin composition, had poor cleanability. Further, it was also clear that the moldability of the resin composition for mold cleaning of comparative example 1 was poor.
It was found that the resin composition for mold cleaning of comparative example 2, in which the ratio of the content of the organic base to the content of the zinc fatty acid was less than 1/100 on a mass basis, had poor cleaning performance.
It was found that the resin composition for mold cleaning of comparative example 3, in which the ratio of the content of the organic base to the content of the zinc fatty acid was greater than 1/2 on a mass basis, was inferior in cleaning property. Further, it was also found that the moldability of the resin composition for mold cleaning of comparative example 3 was poor.
It was found that the resin compositions for cleaning a mold of comparative examples 4 to 6, which contained an inorganic base instead of an organic base, had poor cleaning properties.
Of these, it was found that the mold cleaning resin composition of comparative example 4 containing sodium hydroxide as an inorganic base instead of an organic base was inferior in cleaning property. Further, it was found that when the mold cleaning resin composition of comparative example 4 was used to clean the molding die, a contaminating material derived from the mold cleaning resin composition adhered to the molding die due to molding failure, and the molding die was contaminated instead.

Claims (4)

1. A resin composition for cleaning a mold, comprising a melamine resin, a fatty acid zinc and an organic base, wherein the organic base does not include a salt of a strong acid and a weak base,
the content of the zinc fatty acid is 1-5 parts by mass relative to 100 parts by mass of the total solid content of the resin composition for cleaning a mold, the content of the organic base relative to the content of the zinc fatty acid is 1/100-1/2 on a mass basis, and the content of the melamine resin is 55-85 parts by mass relative to 100 parts by mass of the total solid content of the resin composition for cleaning a mold.
2. The resin composition for mold cleaning according to claim 1, wherein the organic base contains at least 1 compound selected from the group consisting of guanidine compounds and amidine compounds.
3. The resin composition for mold cleaning according to claim 1 or 2, wherein the fatty acid zinc contains at least one selected from the group consisting of zinc myristate and zinc stearate.
4. The resin composition for mold cleaning according to claim 1 or 2, wherein the melamine resin contains a melamine-formaldehyde resin.
CN201710156947.5A 2016-03-18 2017-03-16 Resin composition for cleaning mold Active CN107418141B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016055785A JP6715627B2 (en) 2016-03-18 2016-03-18 Mold cleaning resin composition
JP2016-055785 2016-03-18

Publications (2)

Publication Number Publication Date
CN107418141A CN107418141A (en) 2017-12-01
CN107418141B true CN107418141B (en) 2021-06-15

Family

ID=59973682

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710156947.5A Active CN107418141B (en) 2016-03-18 2017-03-16 Resin composition for cleaning mold

Country Status (5)

Country Link
JP (1) JP6715627B2 (en)
KR (1) KR102291077B1 (en)
CN (1) CN107418141B (en)
SG (1) SG10201702085RA (en)
TW (1) TWI725136B (en)

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0742409B2 (en) * 1987-11-27 1995-05-10 株式会社東芝 Mold cleaning body and mold cleaning method
JP3781445B2 (en) * 1994-08-24 2006-05-31 日本カーバイド工業株式会社 Mold cleaning resin composition
JP3783042B2 (en) * 1995-08-23 2006-06-07 日本カーバイド工業株式会社 Mold cleaning resin composition
JP3270315B2 (en) * 1995-10-31 2002-04-02 日本カーバイド工業株式会社 Mold cleaning resin composition tablet
TW320600B (en) * 1995-10-24 1997-11-21 Nippon Denseki Kogyo Kk
TWI223657B (en) * 2000-10-18 2004-11-11 Chang Chun Plastics Co Ltd Amino resin composition for the cleaning of the mold
JP5604822B2 (en) * 2009-07-17 2014-10-15 日立化成株式会社 Semiconductor device molding die cleaning composition, semiconductor device molding die cleaning material, and semiconductor device molding die cleaning method using the same
KR101788859B1 (en) * 2009-07-17 2017-10-20 닛토덴코 가부시키가이샤 Mold cleaner composition and mold cleaning material, and method of cleaning using the same
JP5972266B2 (en) * 2011-07-15 2016-08-17 日本カーバイド工業株式会社 Mold cleaning resin composition
CN104985903B (en) * 2015-07-31 2017-01-25 北京新福润达绝缘材料有限责任公司 Preparation method for high anti-tracking halogen-free flame-retardant glass-cloth laminate
JP7042409B2 (en) * 2018-03-27 2022-03-28 株式会社サム技研 Selective collating system

Also Published As

Publication number Publication date
TWI725136B (en) 2021-04-21
KR20170108855A (en) 2017-09-27
SG10201702085RA (en) 2017-10-30
KR102291077B1 (en) 2021-08-18
CN107418141A (en) 2017-12-01
TW201800203A (en) 2018-01-01
JP6715627B2 (en) 2020-07-01
JP2017170632A (en) 2017-09-28

Similar Documents

Publication Publication Date Title
KR101934065B1 (en) Mold-cleaning resin composition
KR100305180B1 (en) Amino resin composition for mold cleaning
CN107418141B (en) Resin composition for cleaning mold
KR102019456B1 (en) Resin composition for cleaning die
KR100545249B1 (en) Resin composition for mold cleaning
KR20170113263A (en) Resin composition for cleaning die
JP7265495B2 (en) Mold cleaning resin composition
JP6913038B2 (en) Resin composition for mold cleaning
CN106433021B (en) Resin composition for cleaning mold
JP3847259B2 (en) Mold cleaning resin composition
KR20150056189A (en) Environment-friendly phenol free mold cleaning compound
JPWO2003061935A1 (en) Mold cleaning resin composition
JP2016049693A (en) Resin composition for cleaning mold

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant